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331 Chapter 3
331 Chapter 3
331 Chapter 3
InorganicChemistryII
(Organometallics)
Part1:MainGroupElements
Spring1999
MichaelK.Denk
Chapter3
OrganometallicCompoundsofBoronandAluminum
OrganicCompoundsofBoron
Thestudyofelectrondeficientboroncompoundshascontributedsubstantiallytoour
understandingofthechemicalbond.
ResearchonboroncompoundshasultimatelyledtotwoNobelPrizes:
H.C.Brownforthedevelopmentofthehydroborationreaction(NobelPrizein
Chemistry1979)
WilliamN.Lipscombforhisinvestigationsofstructureandbonding(NobelPrize
inChemistry1976)
Thegreatvalueofthehydroborationreactionliesinthelargenumberoffunctional
groupsthatcanbeintroducedviaboranes.H.C.sharedhisNobelPrizewithG.Wittig/
whodevelopedthechemistryofphosphorusylides("WittigReagents").
H.C.Brown
G.Wittig
W.N.
Lipscomb
WittigReagents
Wittigreagentsareaccessiblefromphosphines(R=alkyl,aryl)orphosphites(R=
alkoxy)intwosteps:
WittigReagentsarehighlyreactiveusuallygeneratedinsitu.Mesomericallystabilized
Wittigreagentscanbequitestableandaresometimesevenavailablecommercially:
ReactivityofOrganoboranes
OrganoboranesR3BareverystrongLewisacidsandreadilyreactwithamines,etc
togivecrystallineLewisacidbaseadducts.
IncontrasttothedimericB2H6(BHBbananabonds)andtheusuallydimeric
organoalanesR3Al,organoboranesR3Barealwaysmonomeric(R2BHdimerize
likeB2H6).Themonomericnatureoforganoboranesmakestheirchemistryless
complexthanthechemistryofhydridoboranesandorganoaluminumcompounds.
Organoboranesareextremelyreactivetowardsoxygenandmoisture.
Organoboranesarecovalentcompounds.Theyaresolubleinhydrocarbonsandcan
usuallybedistilled/sublimed.
OrganoboranesFromHaloboranes
OrganoboranescanbeobtainedfromboronhalidesandGrignardreagents:
BF3Et2O,afumingliquidthatcanbedistilledwithoutdecomposition(doesnotattack
glass)istheleastexpensiveboronhalide
BCl3isalowboilingliquidandmoredifficulttohandle.Moreimportantisthefactthat
BCl3,BBr3,andBI3decomposeethersveryrapidly(BCl3<BBr3<BI3).Thisis
problematicbecauseGrignardreagentsrequireethersfortheirformation
Ofmuchgreaterimportanceisthehydroborationreaction.
OrganoboranesviaHydroboration
ThehydroborationreactionwasdevelopedbyH.C.Brown,agraduatestudentof
SchlesingerwhowasoneofthepioneersofboronchemistryintheUS.
Theimportanceofthehydroborationreactionliesinthemanyusefulreactionsof
organoboranes.
StereoselectivityandRegioselectivityoftheHydroboration
ThehydroborationisanantiMarkovnikovcisaddition:
HydroborationandtheRelativeStabilityofOlefins
Thehydroborationofolefinsisarapidreaction,evenatr.t.
At100200oC),thehydroborationbecomesreversible.Ifthereismorethanone
possibleolefin,amixtureofolefinswillresult:
IfolefinsareheatedwithcatalyticamountsofaboraneR2BH,theresultingmixtureof
olefinswillreflecttheirrelativethermodynamicstability.Thestabilityofolefins
increaseswiththenumberandlengthofalkylgroupsonthedoublebond:
Ifthereactionofanolefin(ormixtureofolefins)isconductedwithstoichiometric
amountsofR2BH,theresultingequilibriummixturewillbedominatedbythemost
stableborane:
Consequently,itispossibletoisomerizedoublebonds"thermodynamic"and"anti
thermodynamic"
BoronasPartofAromaticSystems
Theemptypzorbitalofboroncanbepartofdelocalized,aromaticsystems.Particularly
interestingisthecaseof"borazine"acompoundthatisisoelectronicwithbenzene(the
pairNBisequivalenttoaCCdoublebond):
AllsubstituentsXwithalonepairstabilizetheemptypzorbitalonboronthrough
intramolecularbackdonation.Themagnitudeofbackdonationdecreasesintheseries
R2N>RO>F.
Asaresult,trisalkoxyboranes(RO)3Bandtrisaminoboranes(R2N)3Bdonotshowany
tendencytocoordinateLewisbases.
BackDonationandtheDipoleMomentofBXbonds
Themesomericpresentationofthepbackdonationsuggestsastrongnegativepartial
chargeonboron,andastrongpositivepartialchargeonthedonorsubstituent:
Theexperimentaldeterminationofdipolemomentsshows,thatthepartialchargesare
actuallyquitesmallandthatboronisactuallythepositiveendofthedipole.Thisseems
incontradictionwithourmesomericpresentationofintramolecularpbackdonation.
Themesomericpresentationonlyshowstheshiftingofpelectrons.Therearrangement
ofpelectronsismorethancompensatedbythepolarizationofthesigmaframework,
withtheresultthatthenetchangeofelectrondensitymakesnitrogenthenegativeend
ofthedipole:
Thisseemssomewhatsurprisingbutremember:nitrogenismoreelectronegativethan
boron.
Bearinmindthesigmaeffectswhenyoufeeluncomfortablewithsuchseemingly
unrealisticmesomericstructuresastheoneoftheazideion:
BoroninAromaticpSystems:Boratabenzene
Inviewofthedelocalizednatureofborazine,itwouldseemstraightforwardtoreplace
sp2hybridizedcarboninforexamplebenzenebyaBRunit.
Theresultingboraaromaticcompoundsarehoweverextremelyreactiveandrequire
bulkysubstituentstohavesomedegreeofstability.
Borabenzeneishighlyreactive,butboratabenzeneisknown:
Thesuffixesateandataindicateanionswithincreasedcoordinationnumberfor
cationswithincreasedcoordinationnumbertheendingisonium.
ReactivityofOrganoBoranes
ComparedtoorganiccompoundsR3CRandaminesR3N:,theveryhighreactivityof
organoboranesR3Bmayseemsomewhatsurprising.
ThehighreactivityofboranesiseasiertounderstandifoneconsidersthatboranesR3B
areisolobaltocarbeniumions:
Thetermisolobalwasintroducedtodescribethefactthatcertaincompoundshavevery
similarorbitalsirrespectiveofthedifferentelementsthatareinvolved.
Amoreprecisedefinitionstatesthattwocompoundsareisolobaliftheyhavethesame
energy,symmetryandspatialextensionofHOMOandLUMO.
BoranesandIRSpectroscopy
Boranesareeasilyidentifiedbyinfraredspectroscopy.TheBHbondsabsorbinaregion
ofthespectrumwhereveryfewotherfunctionalgroupsabsorb.IRSpectroscopyis
particularlyimportanttodistinguishbetweenbridging(=nonclassical=3c,2ebond=
"bananabond")andterminalBH:
TheoverwhelmingmajorityofboranescontainsbridgingBHBbonds.TerminalBH
bondsareonlyobservedforboranesR2BHwithverylargesubstituentsR.
TheRelativeStabilityofDoubleBonds
Inviewoftheprominentroleofdoublebondsinorganicchemistryoneistemptedto
taketheexistenceofstabledoublebondsforgranted
However,stabledoublebondsaretheexception,nottheruleasevenasurveyofC=E
doublebondsreveals:
Mg=C
B=C
Al=C
C=C
Si=C
Ge=C
N=C
P=C
As=C
O=C
S=C
Se=C
Sn=C
Pb=C
Sb=C
Bi=C
Te=C
Po=C
E=Ccommerciallyavailablecompounds
E=Cstablewithspecialsubstituents
E=Cnonexistent
TheBoronCarbonDoubleBond:ACaseStudy
Compoundswithaboroncarbondoublebondwereobtainedonlyfairlyrecentlyby
Nthetal.:
Thefinalstepofthesynthesisprovedtobeunusuallydifficult:thetaskwastofinda
basethatwouldleadtothedeprotonationof3withoutreactingwiththehighlyreactive
BClbond.
TMP=2,2,6,6Tetramethylpiperidine,seebelow
NonnucleophilicBases
Thesolutionofthisverygeneralproblemistofindabasesthatareverygoodbasesbut
poornucleophiles.
Thiscanbeachievedbyshieldingthebasewithlargesubstituents:
Thelithiumsaltsoftheabovementionedbasesarecommerciallyavailableasstock
solutions(withtheexceptionoftBu2NLiforwhichneitherthelithiumsaltnorany
otherderivativeiscommerciallyavailable).
Kineticvs.ThermodynamicAcidity
Acidityisrelatedtotheequilibriumconstantofthedeprotonationreactionand
thereforeathermodynamicterm.Withverybulkybases,itispossiblethedifferent
speedsofdeprotonation("kineticacidity")canbecomevisible.
Afamousexampleisthedeprotonationofcyclohexanones:
catenaPolyboranes
Inviewofthevastnumberofelectrondeficientborohydrideclusters,thesmallnumber
ofelectronpreciseboronchainsseemssurprising.
ThehightemperaturereactionofboronwithBCl3givessmallamountsofB2Cl4.The
compoundismoderatelystableandslowlydecomposestoBCl3andamixtureofthe
(nonclassical)closoclusters(BCl)n(n=4,5,6,7,8,9)
Chainsofboronatomsareknowknownwithupto8boronatoms.Theyrequirethe
steric/electronicstabilizationofdialkylaminogroups.Thesystematicsynthesisofthe
catenapolyboraneshasbeenlargelydevelopedbyNthetal.inMunich(1960+).
Startingmaterialsaretheelectronprecisediboranes(4)
Diborane(4)
Unlikediborane(6)withitselectrondeficient2electron3centerbonding,the
diboranes(4)areelectronprecisecompoundsR2BBR2withaboronboronsinglebond.
TheyareobtainedbythereductivecouplingofhaloboranesR2BHaltogive
diboranes(4),areactionthatisrestrictedtodiaminohaloboranesanddialkoxy
haloboranes:
Thethermalstabilityofthediboranes(4)isstronglydependentonthenatureofthe
substituentR:
R=R2N>RO>F>Cl~Alkyl
Alkyl/ArylDiboranes(4)
Dialkylordiarylchloroboranescannotbesuccessfullydehalogenatedbecausethe
productboranesR4B2aremoreeasilyreducedthenthestartingmaterialR2BCl:
InthepresenceofMe3N,thereductionofthediboraneisblockedbytheformationofa
Me3Nadduct:
Tetraalkylandaryldiboranes(4)canbeobtainedfromtetramethoxydiborane(4)and
lithiumorganyls.
ThermalStabilityofDiboranes(4)
Thetetraalkylderivativesaremuchlessstablethanthediboranesbearingdonor
substituentsandcantypicallynotbedistilledwithoutdecomposition.Thenatureofthe
decompositionreactionsisunclearbutalkenesareamongthethermolysisproducts
Thealkylderivativesareobtainedfromtetraaminodiboranes(4)throughthesequence
Halogen/NR2exchange
alkylation
StandardreagentsfortheHalogen/NR2exchangereactionarePCl3andAcetylchloride,
thealkylationsareusuallyperformedwithRLiatlowtemp.(60oCorlower).
catenaPolyboranesfromDiboranes(4)
Longerchainswereobtainedfromtetraaminoderivativesasfollows:
cycloPolyboranes
Itisinterestingtonote,thatboranes(BX)naretypically(nonclassial)closoclustersbut
a(classical)ringgeometrywouldalsobecompatiblewithcompoundsoftype(BX)n
ThedehalogenationofEt2NBCl2hasledtothefirstexampleofaclassicalnonclassical
rearrangementinthepolyboranefield:
Thedimethylaminosubstitutedcyclohexaboranedoesnotshowanytendencyto
rearrangeintoacluster
H.Nth,H.Pommerenning,Angew.Chem.1980,92,481.
OrganicCompoundsofAluminum
Thefirstaluminumorganiccompound,Me3Alwasobtainedfromaluminumand
dimethylmercuryasearlyas1865.Itisremarkable,thattheauthorsalreadydescribed
thiscompoundas"associated."
G.B.Buckton,W.Odling,Annalen,(Suppl.),1865,4,109Proc.Roy.Soc.1865,
14,19.
UseofOrganoaluminumCompounds
Fromanindustrialview,theorganiccompoundsofaluminumarethemostimportant
organometalliccompounds.Thishasthefollowingreasons:
inexpensivesynthesisfromolefin+H2+Al(pressure).
R3Alcandimerizeolefins
higheralcohols(>detergents)aremadefromR3Al+CH2=CH2.
IncombinationwithTiandZrcompounds,R3Alpolymerizeethylenetogive
polyethylene
ReactionswithR3Alproceedinhydrocarbonsorevenwithoutsolvent(difference
fromRMgX!).
PropertiesofOrganoaluminumCompounds
Aluminumorganiccompoundsarecovalent,usuallydimerizedR6Al2(2bridgingR,
differencefromboron)andspontaneouslyflammableinair.Manyofthemcanbe
distilled,buteliminationofolefinscanoccurathighertemperatures.
SynthesisofOrganoaluminumCompounds
Manyaluminumorganiccompoundsarecommerciallyavailableatveryreasonable
prices.Itisthereforerarelynecessarytomaketheminthelaboratory.
ReactionofAlturningswithorganichalidesleadstothealkylaluminumsesquihalides.
Thereactionisveryexothermic.Thesesquihalidesdonothavesharpmeltingorboiling
pointsbecausetheyareinfactequilibriummixtures:
Thesesquihalidescanbetransformedintothetrialkylaluminumorganiccompounds
bereducingthemwithNa.
ForR>Me,anexcessofNamustbeavoided,becauseR3AlcanalsoreactwithNa:
TechnicalSynthesis(I):Me3Al
Thedisproportionationofsesquichloridesisusedinthetechnicalprocessforthe
manufacturingofMe3AlandEt3Albythe"HlsProcess":
TheadditionofNaClisatricktodecreasethechlorinecontentofthemixtureby
precipitatingNa[MeAlCl3].
ThisreducestheamountofsodiummetalrequiredforthereductiontoMe3Al.
TechnicalSynthesis(II):TheZieglerDirectProcess
KarlZiegler,whopioneeredbasicresearchinthefieldofaluminumorganiccompounds
developedastrikinglysimpleyetversatileprocessforthesynthesisofaluminumorganic
compoundsfrominexpensivestartingmaterials.
TheZieglerDirectProcessallowsthesynthesisoftriethylaluminumfromaluminum
metal,hydrogenandethylene.Theprocessinvolvestwosteps.
Thisprocesshasnotonlycreatedaclassofinexpensiveandhighlyreactive
organometallicreagentsbuthasalsocreatednolessthanthreeentirelynewbranchesof
thepetrochemicalindustry:
synthesisofstraightchainalcoholsfromethylene
inexpensivedetergents
synthesisofaolefins
inexpensivepolyethylene
ThebasicresearchofKarlZieglerhasultimatelycreatedanentiremultibilliondollar
industryandallowstheproductionofagreatvarietyoforganiccompounds.
Ziegler'sresearchhasledtooneofthemostdramaticshiftsinthechemicalindustry,the
transitionfromcoalandacetylenetoethylene.
Theimportanceofhisresearchwassoonrecognizedandhereceivedthe1963Nobel
PrizeforChemistry,togetherwithGiulioNattawhomadefundamentalcontributionsto
thepolymerizationfield.
DetergentsfromOrganoaluminumCompounds
Detergentsareamphiphilicmoleculeswithahydrophilicfunctionalgroupanda
lipophilicchain.Theyhavetheabilitytoformlipophilicpocketsinwaterandthushelp
tosolubilizeorganicmaterialsinwater:
Traditionalsoapsareobtainedbythehydrolysis("saponification")ofplantoranimal
fat.Thehydrolysisproductsareglycerolandfattyacids.Thesaponificationisconducted
withNaOH(washingsoap)orKOH(softsoap).
Soapswithcationicendgroupsarequitetoxictomicroorganismsandareusedas
antibacterialsoapsinhospitalsetc.
LaundryandkitchendetergentsaremanufacturedfromC10C16alcohols(fromEt3Al+
ethylene)andsulfuricacid:
AmidesofBoronandAluminum
Aspreviouslydiscussed,boronformsanextensiveseriesofaminocompoundsthat
containtheunitBN,isoelectronicwithC=C.Thegoodoverlapbetweentheemptypz
orbitalonboronandthelonepaironnitrogenfavorsintramoleculardativebonds.
Foraluminum,theoverlapbetweentheemptypzorbitalandthenitrogenlonepairis
notasgoodandnitrogenaluminumcompoundspreferintermoleculardativebonds.
Thisleadstotheformationof(R2AlNR'2)ncageswithntypically24.Thenumberof
AlNunitsinthecagesisdeterminedbythesizeofthesubstituentsR.Largesubstituents
favorsmalleraggregates
ComplexHydrides:History
ComplexhydrideswerefirstinvestigatedbySchlesingerwhowasthen(19421945)a
partoftheUSwareffortstobuildanatomicbomb.Heinvestigatedthecompound
U(BH4)4,asavolatileuraniumcompoundtobeusedfortheseparationof235Ufrom
238Ubygasdiffusion.
Complexhydrideshavesincebecomethesyntheticchemist'smostvaluablereducing
agents.
Manyreductionsthatpreviouslyrequiredhightemperaturesandpressuresand
catalystscannowbedoneatstandardpressureandtemperature.
EquallyfarreachingwasthediscoveryofthehydroborationreactionbyH.C.Brown,
oneofSchlesinger'sstudents.
ComplexhydridesofaAluminumandBoronarenowmanufacturedonascaleof10,000
100,000to/a.
TheHydridesMH3
ThehydridesMH3canbeobtainedfromthecomplexhydridesbytheadditionofacid:
Thesereactionshavetobeconductedinanhydrousmedium(Et2Oetc.)becauseB2H6
butespeciallyAlH3reactwithwater.Betteryieldsareobtainedbyreactingthehalidesof
thecorrespondingelementswiththecomplexhydrides:
StabilizationofMH3
WiththeexceptionofB2H6,theyarenotparticularlystable.Alane,AlH3,isapolymeric
solidthatcanbestabilizedbythecoordinationofLewisBases:
SolutionsofB2H6andtheTHFcomplexTHF>BH3arecommerciallyavailable.
ComplexHydrides:ThermalStability
ThehydridesMH3cannotonlybestabilizedbythecoordinationofethersandamines
butalsobytheadditionofhydrideiontoformthecomplexanion[MH4].
Thethermalstabilityofanions[MH4]decreasesintheorderB>Al>Ga:
Compound
Decomposition
LiBH4
LiAlH4
LiGaH4
LiInH4
LiTlH4
380
oC
100oC
50oC
~0oC
~0oC
HazardsinWorkingwithLiAlH4
ThedissolutionofLiAlH4inethersisafairlyexothermicprocess.Addingetherstolarge
quantitiesofLiAlH4(insteadoftheotherwayround)canleadtolocaloverheatingand
explosions,especiallyiftheethercontainswater.
ComplexHydrides:Solubility
ThelithiumsaltsLiAlH4andLiBH4haveasurprisinglyhighsolubilityinethersbutthe
sodiumsaltsareinsoluble.
ThisisattributedtoaspecificinteractionbetweenLi+,AlH4andthesolvent,namely
thecomplexationofthestronglyLewisacidicLicationbyether:
Thecomplexhydridesdifferintheirreactivitytowardswater.LiAlH4andNaAlH4react
explosivelywithwater(formationofH2,LiOHandAl(OH)3).
Theborohydridesdissolveinwaterwithoutdecomposition.Thestabilityofthesolutions
ispHdependent:belowpH7,theborohydridesolutionsdecomposerapidly,abovepH9
thedecompositionbecomesveryslow.SolutionsofNaBH4canthereforebestabilizedby
theadditionofNaOH.
Sodiumcyanoboroydride,Na[BH3CN]isevenmoreresistanttoacidicconditionsand
canbesafelyhandleddowntoapHof4.
ThegoodsolubilityandstabilityofNaBH4inwatermakesitanindispensablereducing
agentsforall"hydrophilicjobs"(reductionofsugarsetc.)
ComplexHydrides:Synthesis
Theindustrialsynthesisofthecomplexhydridesproducesthesodiumcompounds,the
lithiumcompoundsarethenmadebysimplemetathesisofthesodiumsaltswithLiCl.
Aluminumisreactiveenoughthebeusedasstartingmaterial,butelementalboronis
bothveryunreactiveandexpensive.Theinexpensivetrimethoxyborate,B(OMe)3,is
usedinstead.)
CommerciallyavailableNaAlH4orLiAlH4isusuallygrayishincolor(aluminumdust
fromthemanufacturingprocess),thepurecompoundsarewhite.
ComplexHydridesinInorganicSynthesis
Theavailabilityofcomplexhydridesmakesthesynthesisofotherelementhydrides
straightforward.
TheKumadaNegishiCoupling
Alkenylaluminumcompoundsareeasilyaccessiblefromalkynes+R2AlH.Theycanbe
crosscoupledwithvinylbromidestogive1,3dienes.
ThereactioniscatalyzedbyPdorNiandishighlystereospecific.
Methyl(E,E)2methyl2,4nonadienoate(3).[1]
Todichlorobis(triphenylphosphine)palladium(0.74g,1mmol)inTHF(20mL)were
addedsequentiallyneatdiisobutylaluminiumhydride(0.37mL,2mmol)(10minat25
oC),(E)lhexenyldiisobutylalane1(obtainedfrom1hexyne(1.64g,20mmol)in
hexane(20mL)anddiisobutylaluminiumhydride(3.58g,20mmol).Methyl(E)3
bromo2methylpropenoate2(3.58g,20mmol)wasadded(25oC)andthemixture
wasrefluxedfor15min.Afteradditionof3NHCl,extractionwithEt20,drying
(MgS04)andevaporationofthesolvent,distillationafforded2.2gof3(61%),bp78
79oC/lTorr.
References
1. Negishi,E.J.Am.Chem.Soc.1976,98,6729.
2. Kumada,M.Pure.Appl.Chem.1980,52,669.
3. Negishi,E.Acc.Chem.Res.1982,15,340.
4.Negishi,E.J.Am.Chem.Soc.1987,109,2393.
5. Negishi,E.Synthesis1988,1.
Gallium
Theelementgalliumisrareandcomparativelyexpensive.Galliumarsenide(GaAs)is
nowuniversallyusedthebasematerialforlaserdiodes(CDplayersetc).Gallium
arsenidecannowbedepositedinmicroelectronicqualityfromGaMe3:
TheGallexDetector
Galliumistheelementwiththehighestcapturecrosssectionforneutrinos.Thishas
beenusedtobuildoneofthemostbizarreparticledetectorsofcontemporaryphysics,
theGallexdetector.
LowValentGroup13Compounds
Galliumisalsothelightestelementingroup13thathasasubstantiallowvalent
chemistry.IfGaCl3isreactedwithGaatelevatedtemperaturesforafewdays,themetal
dissolvescompletelyandagrayishwhitesolidofformulaGaCl2isobtained.
ThisgalliumsubchlorideisinfactamixedvalentcompoundGa(I)/Ga(III)compound
Ga+[GaCl4].Thecompoundissurprisinglysolubleinbenzene,afactthatcanbe
attributedtothestrongpcomplexationofaromatichydrocarbonswithGa+.
XraystructuresofGa+arenecomplexesresemblethecomplexesoftransitionmetals,
buttheareneunitsarerapidlyexchangedinsolution.ThestabilityofM+complexes
decreasesinthesequenceGa>In>Tl.
TrulydivalentgalliumcompoundsoftypeR2GaGaR2havebeenobtainedfrom
reductivedehalogenationofR2GaCl.
continuedinchapter4:OrganometallicChemistryofGroup14Elements